Ceramics International 28 (2002) 617–621

www.elsevier.com/locate/ceramint

Sintering effects on mechanical properties of glass-reinforced

hydroxyapatite composites
Faik Nüzhet Oktara, Gültekin Göllerb,*
a
.
Marmara University, New Technologies, R & D Center, Ziverbey, Istanbul, Turkey.
b
Istanbul Technical University, Metallurgical and Materials Engineering Department, Maslak-Istanbul, Turkey

Received 26 June 2001; received in revised form 18 July 2001; accepted 8 November 2001

Abstract
The improvement of mechanical properties of hydroxyapatite (HA) with reinforcement of two (45.5 wt.% P2O5, 54.5 wt.% CaO)
and three-oxide (45 wt.% P2O5, 28 wt.% CaO, 27 wt.% Na2O) glasses with different sintering temperatures is studied. Although
HA shows great biocompatibility with the human body, its applications are limited to non load-bearing areas and coatings due to
its low mechanical properties. These mechanical properties can be improved substantially with addition of glass ceramics by sin-
tering. In this study, naturally produced HA from human teeth is sintered with varying addition of two and three-oxide glass
ceramics. The microhardness measurements, the density and the compression tests are performed in order to find the optimum
sintering temperature. Finally average hardness value of 285
19 HV, average density of 2.79
0.05 g cm3 and compressive
strength value of  avr=67
17 MPa have been achieved by sintering at 1200  C with the addition of 10 wt.% two oxide glass into
the HA. Results are implying that 10 wt.% of glass addition for HA composites is the maximum limit for such composites.
Observations are supporting the idea that sodium free glasses could be better conciliated with the HA structure at high tempera-
tures. # 2002 Elsevier Science Ltd and Techna S.r.l. All rights reserved.
Keywords: A. Sintering; B. Composites; D. Glass ceramics; Hydroxyapatite

1. Introduction properties. In return, compared with the monolitic

Bioactive ceramics, such as bioglass and dense
hydroxyapatite (HA), have been developed over the last
two decades. Their accomplishments in the field of bio-
medical applications, especially in prosthetic applica-
tions, have attracted wide attention [1]. Calcium
phosphate ceramics, especially HA, are currently used
as biomaterials for many applications in both dentistry
and orthopedics, because they form a real bond with the
surrounding bone tissue when implanted. Nevertheless,
due to the poor mechanical properties of bulk HA
ceramics, such materials cannot be used as implant
devices for load-bearing applications [2]. On the other
hand it is well known that the incorporation of a cera-
mic reinforcement (i.e. fibres, whiskers, platelets or par-
ticles) in a ceramic matrix improves the mechanical
* Corresponding author. Tel.: +90-212-285-6891; fax: +90-212-
285-3427.
E-mail address: goller@itu.edu.tr (G. Göller).
0272-8842/02/$22.00 # 2002 Elsevier Science Ltd and Techna S.r.l. All rights reserved.
PII: S0272-8842(02)00017-2
matrix behavior, the presence of a reinforcement oppo-
ses the sintering process [3]. Sintering is the term used to
describe the consolidation of the product during firing.
Consolidation implies that within the product, particles
have joined together into strong aggregate. The term
sintering is often interpreted to imply that shrinkage
and densification have occurred. Sintered HA implants
are observed to develop cracks. Thus, an optimization
of the strength and microstructure of HA implants by a
suitable choice of sintering parameters are needed.
Glasses within the P2O5–CaO–Na2O system possess
enormous potential as biomaterials, because their com-
positions are similar to that of the inorganic constituent
of the mineral part of bone [4]. All constituents of
bioactive glasses could potentially be used as additives
to HA ceramics to improve properties of the HA cera-
mic [5]. In experimental studies related to the reinforce-
ment of HA, it is observed that glass-reinforced HA
composites exhibit greater biological activities than
commercial HA [6]. The purpose of this research is
to determine variation of mechanical properties of
618 F.N. Oktar, G. Göller / Ceramics International 28 (2002) 617–621

biologically derived HA–glass composites depending on
reinforcement content and sintering temperature.
2. Materials and experimental procedure
2.1. Production of HA
polyvinylalcohol was not used. All materials were kept
out for a couple days in normal atmospheric conditions
and kept slightly humid. It was observed before that
sintered powders would not compact together due to the
lack of humidity [8]. Pressed samples were sintered in an
open atmospheric oven up to temperatures 1200  C, and
1300  C with a heating rate of 4  C per minute.

The HA material used in this study was derived from
freshly-extracted human teeth. The teeth were irrigated
with tap-water [7] and soaked in a 1 wt.% concentration
of antiseptic solution to prevent bad odor and con-
tamination of various infectious diseases. Subsequently
the teeth were reirrigated and deproteinized in an alkali
solution (1% concentration of sodium hypochloride).
Thereafter samples were reirrigated with tap-water
again. All samples were heated to 850  C with a heating
rate of 5  C min1 and kept at that temperature for 5–6
h. Easily separation of the dentine and enamel matter
have been observed at that temperature, and approxi-
mately 60% of the material was dentine and 40%
enamel. Enamel and dentine parts were subjected to
grinding with a blade grinder for 30 s. Following this
resulting samples were then sieved and only dentine
based HA particles with a particle size of 106–150 mm
were used in this research [7].
2.2. Preparation of bioglass compositions
Phosphate-based glasses with the chemical composi-
tions listed in Table 1, were prepared from reagent
grade chemicals P2O5, CaCO3 and Na2CO3 (Merck
Ltd.) as described by Santos et al. [4]. Chemicals were
placed in a platinum crucible and heated at 1200  C for
3 h. Once the glass was poured, it was milled to a pow-
der-type particle in a porcelain ball mill for 24 h. Ace-
tone (Merck Ltd.) and HA were wet milled together
further for 24 h, and then HA and glass compositions
were ball milled with acetone together with a varying
amount of reinforcement content.
2.4. Mechanical testing
The density of sintered samples was determined by the
Archimedes method. Vickers hardness values were
obtained using a Shimadzu microhardness testing
machine with 100 g load. Compression test according to
British Standard 7253 were carried out with a universal
test machine (Instron 1195) at a cross head speed of 2
mm min1. All tests were performed to at least 10 spe-
cimens and their averages were taken as the main
measurement.
3. Results
Density, compression and microhardness tests results
for HA–glass composites are listed in Tables 2 and 3.
Results indicated that HA–glass composites have sig-
nificantly higher density values compared to HA sin-
tered bodies reported previously [9]. In that study
densities of sintered pure HA were found 2.59 and 2.48
g/cm3 at 1200–1300  C respectively, whereas densities of
HA-glass composites varied about from 2.81–2.77 g/cm3
depending on glass type reinforcement and sintering
temperature (Tables 2–3). Experimental data are
strongly supporting the idea of existence a very good
Table 2
Sintering results of HA and two-oxide glass composites in two sinter-
ing temperatures
Temperature avr  avr Hardnessavr
( C) and (%) (gr cm3) (MPa) (HV)

2.3. Sample preparation 1200 (5) 2.81
0.12 64
27 250
19

1200 (10) 2.79
0.05 67
17 285
19
1300 (5) 2.77
0.05 39
9 238
26
A die was designed to prepare samples with a dia- 1300 (10) 2.76
0.05 53
11 279
12
meter of 11 mm according to British Standard for com-
pression tests no. 7253. The powders were weighed to
total 3.25 g. portions. The prepared portions were uni-
Table 3
axially pressed at 350 MPa between hardened steel Results of HA and three-oxide glass composites in two sintering tem-
dies (die height 5 mm). In this study no lubricant like peratures

Table 1 Temperature avr  avr Hardnessavr

Chemical composition (mol%) of phosphate-based glasses ( C) and (%) (gr cm3) (MPa) (HV)

Glass addition P2O5 CaO Na2CO3 1200 (5) 2.79
0.05 36
11 222
23
1200 (10) 2.76
0.11 40
21 259
15
2 Oxide 45.5 54.5 – 1300 (5) 2.79
0.04 55
14 358
18
3 Oxide 45.0 28.0 27.0 1300 (10) 2.79
0.14 39
12 301
8
 F.N. Oktar, G. Göller / Ceramics International 28 (2002) 617–621 619

wettening between HA particles and glass reinforce-
ment. Sintering of HA is complicated by the fact that
HA is hydrated phase that decomposes to anhydrous
calcium phosphates such as TCP at  1200–1450  C.
Decomposition results from dehydroxylation beyond a
critical point. For temperatures below the critical point
(1300  C), the HA crystal structure is retained despite
dehydroxylation, and the HA rehydrates on cooling. If
the critical point is exceeded, complete and irreversible
dehydroxylation occurs, resulting in collapse of the HA
structure and decomposition. Significant reversible
dehydroxylation generally occurs above  800  C. After
the critical point a-TCP and b-TCP are often formed. In
particular the molecular volume increase that occur in
the b-TCP ! a-TCP transformation seem to be the
most deleterious phenomenon for mechanical properties
[10]. Fig. 1(a) and (b) reveal that increasing sintering
temperature decreases density of composites. A decrease
in density could be attributed to the initation of b-TCP
to a-TCP transformation at that temperature range.
Compression test results of HA/two-oxide glass com-
posites were showed substantially higher strength values
compared to HA sintered bodies. While strengths have
been observed 56 and 56 MPa for HA bodies sintered at
1200 and 1300  C respectively, they were obtained
interesting values of 64 MPa, 67 MPa at 1200  C and 39
MPa, 53 MPa at 1300  C as seen in Table 2. It is observed
from the table that the higher the sintering temperature is
the lower the compression strength. On the other hand
three oxide reinforced HA composites showed lower
strength values compared to two oxide reinforced com-
posites. Compression strength values of three oxide rein-
forced HA system are lower than that of two oxide–HA
composites with respect to corresponding sintering
temperature with an exception corresponding to 5 wt.%
three oxide reinforced composite sintered at 1300  C.
The reason of high standard deviation values also can
be attributed to brittleness character of HA.
Variations of compressive strength depending on sin-
tering temperature and reinforcement content are shown
in Fig. 2a and b. It can be observed that increasing rein-
forcement content increases compressive strength at
constant temperature but the higher the sintering tem-
perature is the lower the compressive strength for two
oxide containing composites (Fig. 2a). On the other hand
this fact is reverse for three oxide composite, the lower
sintering temperature the lower compressive strength.
Increasing the temperature resulted in higher compressive
strength for 5 wt.% reinforcement but for a higher rein-
forcement content, the strength remains low whatever the
sintering temperature. The reason of such an effect will
be discussed in following section.

Fig. 1. Sinterability with (a) two-oxide and (b) three-oxide glass reinforced HA composites at two temperatures.

Fig. 2. Variations in compressive strength in (a) two-oxide and (b) three-oxide glass reinforced HA composites at two sintering temperatures.
620 F.N. Oktar, G. Göller / Ceramics International 28 (2002) 617–621
4. Discussion
Santos et al. have reported that the mechanical prop-
erties of HA can be dramatically increased by the
incorporation of a glassy phase during its sintering
process. The glasses chosen were phosphate-based glas-
ses closely related to the composition of HA. A strong
chemical bond is developed between HA and the phos-
phate-based glasses at high temperatures. The liquid
phosphate phase acted on the solid HA particles to
reduce interfacial energy and promote the kinetics of the
sintering process by a faster atomic diffusion than the
concurrent solid state process of single HA. As a result
of this chemical bonding, TCP phases were formed and
the porosity was eliminated. The presence of a highly
soluble tricalcium phosphate phase, b-TCP, formed
from the reaction between bioglass and the HA matrix
during liquid phase sintering process, induces a much
faster Ca, P formation than HA. These statements are
all in good agreement with our experimental results.
Good wettening between two phases and porosity elim-
ination resulted in increased density and hardness values
(Tables 2 and 3) as compared to HA sintered bodies.
In experimental studies, short sintering time and lim-
ited glass addition such as 2.5–5 wt.%, were used to
control phase transformation between two phases
[11,4,12], and observed that greater amount of phase
transformation occurred with the addition of 5 wt.%
CaO–P2O5 but there were no research available related
to two oxide or three oxide addition into HA up to the
level of 10 wt.% in the literature. It was observed that
the use of CaO–P2O5 type glass for the production of
reinforced HA was significantly benefit to the stabiliza-
tion and the tailoring of high strength values of the HA
(35–88 MPa) [13]. Another crucial point is the behavior
of Na containing glass compositions in HA composites.
It was proposed in a study that Na including glass sys-
tem was not stable above 700  C. The sodium ions dif-
fused from the glass phase into the HA structure which
then transformed into rhenanite. The diffusion process
was not extremely fast and with sufficiently short reac-
tion times that the sodium ions had not reached the
centres of the HA particles [14]. Data indicate that
compressive strengths for two-oxide glass reinforced
HA composites are very good for 5 and 10 wt.% addi-
tion at 1200  C but these values are decreased at
1300  C. It should also be noted that compressive
strength and hardness values of samples containing 10
wt.% two oxide glass is better than for 5 wt.% rein-
forced composites whereas this fact is reverse with
three-oxide glass system of which the hardness is lower
for 10 wt.% glass reinforcement than for 5 wt.%. Lower
values of hardness for three oxide system are indicating
that sodium free two oxide systems are superior to
sodium containing glass systems. All these results and
lower hardness values obtained for three-oxide systems
can be attributed to sodium effect on lattice structure.
These facts are in agreement with Kangasniemi et al.
findings [14].
5. Conclusions
Optimum mechanical properties of HA–glass compo-
sites can be achieved by sintering at 1200  C with the
addition of 10 wt.% two oxide glass into the HA.
Experimental data are implying that 10 wt.% of glass
addition for HA composites is the maximum limit for
such composites. Observations are supporting the idea
that sodium free glasses could be better conciliated with
the HA structure at high temperatures.
Acknowledgements
This work has been carried out by the support of
Istanbul Technical University Research Fund with the
Project Code 1700. The authors would like to thank
Professor Selim Kusefoglu for his contributions during
sintering experiments.
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